Modified polyolefin resin, modified polyolefin resin composition, and uses thereof

ABSTRACT

A resin which has excellent adhesion to nonpolar substrates, is nontacky, and has satisfactory solubility in aromatic or nonaromatic solvents and satisfactory compatibility with other resins. The resin is a modified polyolefin resin having a weight-average molecular weight of 15,000 to 150,000 obtained by modifying a polyolefin resin by grafting thereto (A) an unsaturated polycarboxylic acid or a derivative thereof and (B) a (meth)acrylic ester represented by a specific general formula, the contents of (A) and (B) in the modified polyolefin resin being 0.1 to 20 wt. % and 0.1 to 30 wt. %, respectively.

TECHNICAL FIELD

[0001] The present invention relates to a modified polyolefin resin withimproved adherence onto the surface of substrate, in particular, surfaceof substrate having nonpolar thermoplastic resin as a prime material andimproved solubility into nonaromatic nonpolar solvent, its compositionand uses.

BACKGROUND TECHNOLOGIES

[0002] Utilizing the nature to be transformed by heat, the thermoplasticresins are used as various configurations of commodities by molding intonot only planar shapes such as sheets and films, but also certain shapesof spherical, cylindrical, box-like, etc. However, since thethermoplastic resins are fundamentally transparent, relatively soft andfragile, printing and painting are provided on their surfaces, for thepurpose of improved protection and beautiful ornament.

[0003] The thermoplastic resins include resins with polarity and thosewith nonpolarity. Among nonpolar resins, polyolefinic resins such aspolypropylene and polyethylene are adopted widely in recent years,because of low price and many excellent properties such as moldability,chemical resistance, water resistance, electrical characteristics andsafety. Different from polar resins such as acrylic resin and polyesterresin, however, the polyolefinic resin is nonpolar and crystalline,hence it is difficult to adhere ink, paint or adhesive firmly onto itssurface.

[0004] In opposition to such substrates of nonpolar resins usingpolyolefinic resins, as resins with adherence, acid-modified polyolefinresins, from unsaturated carboxylic acid modification down, areproposed. The acid-modified polyolefin resin has adherence onto thenonpolar substrates, but its adherent strength is low and the coatedfilm after drying has tack. For example, when acid-modified polyolefinresin is coated onto the surface of film-shaped substrate and dried toform film and then it is wound up, problems of clinging of dirts ontothe surface of film and blocking after winding could not be avoided.

[0005] Moreover, the acid-modified polyolefin resin is generally poor inthe solubility into solvent and the compatibility with other differenttypes of resins, hence, usable solvents and mixable other resins wererestricted on manufacturing paint for painting and printing ink,resulting in problems of difficult production of paint, ink, adhesive orthe like with sufficient performance.

[0006] Moreover, in recent years, from the viewpoint of environmentalproblems, such resin that dissolves into solvents containing no aromaticsolvent at all has been explored. However, with respect to the solventsto be used for dissolving conventional acid-modified polyolefin, the useof aromatic solvents such as toluene and xylene is essential, hence itwas very difficult to dissolve into nonaromatic solvents whilemaintaining various physical properties such as adherence by theconventional techniques of acid-modified polyolefin.

[0007] As the means to improve the problems of solubility into solvent,compatibility with other resins, tack of dried film, and the like, amethod of graft copolymerizing two or more unsaturated carboxylic acidsor their derivatives with different properties onto polyolefin resin, asusing unsaturated carboxylic anhydrides and nonanhydrides such as maleicanhydride and acrylic acid in combination, is disclosed in JapaneseUnexamined Patent Publication Nos. Hei 9-40724, Hei 7-82328, Hei3-227341, Hei 2-245042, etc. Moreover, in addition to the method ofsimple graft polymerization, a method of modification by furtherreacting polyester, alcohol, etc., after graft copolymerized unsaturatedcarboxylic acids or their derivatives such as acrylic acid and maleicanhydride onto polyolefin, is proposed in Japanese Unexamined PatentPublication No. Hei 11-217537. It is reported that the modifiedpolyolefin resin obtainable by this method can improve the solubilityinto solvent, stability of solution on storing for a long term, etc.

[0008] However, when graft copolymerizing monomers of unsaturatedcarboxylic acids or their anhydrides such as acrylic acid and maleicacid onto polyolefin resin, in particular, polyolefin resin with highpropylene content, it is known that the degradation (decrease inmolecular weight) is accompanied [Journal of Polymer Science 33, 829(1995) etc.]. With the modified polyolefin resin obtainable by modifyingpolyolefin resin with high propylene content by said method, decreasedmolecular weight was brought about, adherent strength onto nonpolarsubstrates was still insufficient, and also the problem of tack offormed film could not be solved.

[0009] On the other hand, it is also well known that, through thealteration of reaction conditions such as increased use level of saidmodifying monomer, increased molecular weight of grafting portion can beaccomplished easily. In this case, however, the solubility intononaromatic solvent improved, but sufficient adherent strength ontohard-adherent nonpolar substrates could not still be achieved, becauseof relative decrease in the content of polyolefin being a majorcomponent for developing adherent strength.

[0010] Moreover, when graft copolymerizing (meth)acrylic acid or itslower alkyl ester with relatively high polarity, homopolymer andcopolymer ungrafting onto polyolefin skeleton were produced in largequantities, resulting in decreased solvent solubility and decreasedsolvent resistance of dried film etc., which did not come to thepractical use.

[0011] As described, with the modified polyolefin resins obtained byconventional methods, the enhancement of adherent strength onto nonpolarresins was insufficient. In particular, onto the high-crystallinehard-adherent polyolefin moldings and untreated polyolefin resinswithout surface treatment for improved adherence such as coronatreatment, the adherent strength was insufficient even in the case ofreinforced adhesive conditions, hence more improvement in the adherentstrength has been desired.

[0012] There, the purpose of the invention is to obtain a resin withexcellent adherence even onto nonpolar substrates, in particular,hard-adherent nonpolar substrates without preliminary surface treatmentfor improving hard-adherence or adherence. Furthermore, it is to providea resin that combines attributes of excellent solubility intononaromatic solvent, good compatibility with other resins, and improvedtack of films obtainable by coating and drying this resin itself orcompositions such as paint and ink containing this resin as well.

DISCLOSURE OF THE INVENTION

[0013] As a result of diligent investigations, the inventors have foundthat, by combinationally using unsaturated polycarboxylic acid or itsderivative and a particular (meth)acrylic ester as monomers forpolyolefin resin and graft copolymerizing to modify, not only saidproblems are solved with use level of monomers of the order of notinjuring the adherent strength, but also excellent adherent strength isexhibited even onto hard-adherent polyolefin moldings and untreatedfilms of polyethylene and polypropylene under broad conditions fromcondition for adhesive treatment at high temperature to condition foradhesive treatment at low temperature of around room temperature to 100°C. Furthermore, in this case, the inventors have found that the modifiedresin has excellent solubility into nonaromatic solvent as well asaromatic solvent, leading to the invention.

[0014] Namely, the invention relates to

[0015] (1) a modified polyolefin resin with polyolefin resin graftmodified with unsaturated polycarboxylic acid or its derivative (A) and(meth)acrylic ester (B) represented by a following general formula, withcontents of (A) and (B) of 0.1 to 20% by weight and 0.1 to 30% byweight, respectively, in modified polyolefin resin, and with weightaverage molecular weight of 15,000 to 150,000,

CH₂═CR₁COOR₂  (Chemical formula 2)

[0016] (wherein R₁═H or CH₃, R₂═C_(n)H_(2n+1), n=integer of 8 to 18)

[0017] (2) the modified polyolefin resin of (1), wherein saidunsaturated polycarboxylic acid or its derivative (A) is itaconicanhydride and/or maleic anhydride,

[0018] (3) the modified polyolefin resin of (1) or (2), wherein said(meth)acrylic ester (B) is at least one kind selected from octyl(meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate andstearyl (meth)acrylate,

[0019] (4) the modified polyolefin resin of any of (1) through (3),wherein said polyolefin resin is at least one kind selected fromethylene-propylene copolymer, propylene-butene copolymer, andethylene-propylene-butene copolymer,

[0020] (5) a modified polyolefin resin composition characterized byformulating curing agent selected from epoxy, polyisocyanate, polyol,polyamine and curing agents with those functional groups blocked withprotective group, to the modified polyolefin resin of any of (1) through(4),

[0021] (6) an adhesive containing modified polyolefin resin of any of(1) through (4) or modified polyolefin resin composition of (5),

[0022] (7) a primer containing modified polyolefin resin of any of (1)through (4) or modified polyolefin resin composition of (5),

[0023] (8) a paint containing modified polyolefin resin of any of (1)through (4) or modified polyolefin resin composition of (5), and

[0024] (9) an ink containing modified polyolefin resin of any of (1)through (4) or modified polyolefin resin composition of (5). Infollowing, the invention will be explained in detail.

[0025] The modified polyolefin resin of the invention is suitable for anadherend having thermoplastic resin, in particular, non-polarthermoplastic resin as a substrate. The nonpolar resins includepolypropylene, polyethylene, ethylene-propylene copolymer,propylene-butene copolymer, ethylene-propylene-butene copolymer, terpeneresin and styrene resin. The modified polyolefin resin of the inventionis characterized in that the adherends having these nonpolar resins assubstrates can be used, even if they may be hard-adherent ones notsubject to the surface treatments with plasma, corona, etc. for improvedadherence. As for the shape of adherends, it is possible to apply to anyof shapes suitable for the use, from planar shapes such as sheets andfilms and spherical, cylindrical, box-like and other shapes down.

[0026] The polyolefin resin of the invention is composed of olefins withnumber of carbon atoms of not less than 2 to not more than 20,preferably not less than 2 to not more than 6 such as ethylene,propylene, butene, pentene, hexene, heptene, octene and4-methyl-1-pentene, and, above all, α-olefins with said number of carbonatoms are preferable. Moreover, homo- or co-polymers of chain or cyclicpolyenes such as cyclopentene, cyclohexene, 1,4-hexadiene,1,5-hexadiene, divinylbenzene, 1,3-cyclopentadiene, 1,3-cyclohexadieneand 5-vinyl-2-norbornene, or styrene, substituted styrene, etc. can beused as the polyolefin resins of the invention. The proportion of thesemonomers in polymer can be selected arbitrarily, but, when hard-adherentnonpolar polyolefin resins such as crystalline polyethylene andpolypropylene are adherends, the inventive modified polyolefin resinsare preferable to be ethylene-propylene, propylene-butene andethylene-propylene-butenecopolymer, and, in particular, the proportionof propylene in these resins is preferable to be not less than 50% tonot more than 98%. If under 50%, then the adherence to adherend is poor,and, if over 98%, the flexibility is insufficient.

[0027] Upon producing the modified polyolefin resin of the invention,the molecular weight of polyolefin resin that becomes starting rawmaterial is not particularly restricted. it is required, however, thatthe weight average molecular weight of modified polyolefin resin aftermodification becomes 15,000 to 150,000. When the molecular weight of rawmaterial polyolefin resin is high, it is possible to adjust themolecular weight to a suitable range by degrading in the presence ofheat or radical, or by degrading at the same time as modificationreaction. Besides, the raw material polyolefin resins can be used solelyor in combination of multiple kinds. Moreover, in the modifiedpolyolefin resin of the invention, the raw material polyolefin isrequired to be not less than 50% by weight.

[0028] The unsaturated polycarboxylic acids or their derivatives (A) areunsaturated polycarboxylic acids such as maleic acid, fumaric acid,tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid,aconitic acid, phthalic acid, trimellitic acid andnorbornenedicarboxylic acid, or their derivatives (e.g. acid anhyride,acid halide, amide, imide, ester, etc.). Thereamong, itaconic anhyrideand maleic anhyride are preferable in the points of various physicalproperties of film of modified polyolefin resin, handling property andcost. The grafting weight of modifying component (A) in modifiedpolyolefin resin is required to be 0.1 to 20% by weight, preferably 1 to15% by weight and more preferably 2 to 10% by weight. If the graftingweight is lower than this range, then the solvent solubility andadherent strength onto substrates of modified polyolefin resin decrease.Also, if too high inversely, much unreacted materials generate, which isunpreferable. Besides, these modifying monomers (A) can be used solelyor in combination of multiple kinds.

[0029] The (meth)acrylic ester (B) is at least one kind selected fromcompounds represented by a following general formula.

CH₂═CR₁COOR₂  (Chemical formula 3)

[0030] (wherein R₁═H or CH₃, R₂═C_(n)H_(2n+1), n=integer of 8 to 18)

[0031] Thereamong, octyl (meth)acrylate, lauryl (meth)acrylate, tridecyl(meth)acrylate and stearyl (meth)acrylate are preferable in the pointsof various physical properties of film of modified polyolefin resin andcost. In the general formula shown above, if n is smaller than 8, thesolvent solubility is aggravated, and, if n is larger than 18, then thetack is caused in film, which is unpreferable. Moreover, the graftingweight of modifying monomer (B) in modified polyolefin resin is 0.1 to30% by weight, preferably 1 to 15% by weight. If the grafting weight islower than this range, then the solvent solubility, compatibility withother resins and adherent strength onto substrates of modifiedpolyolefin resin decrease. Also, if too high inversely, highly reactivemodifying monomer (B) forms ultrahigh-molecular weight material toaggravate the solvent solubility likewise, or production level ofhomopolymer and co-polymer ungrafting onto polyolefin skeletonincreases, which is unpreferable. Besides, these modifying monomers (B)can be used solely or in combination of multiple kinds.

[0032] Moreover, in the invention, depending on the use and purpose,monomers other than modifying monomers (A) and (B) can be used incombination within a range of not injuring the characteristics of theinvention. The usable monomers are, for example, (meth)acrylic acid,(meth)acrylic acid derivative other than (B) (cyclohexyl (meth)acrylate,hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, glycidyl(meth)acrylate, isocyanate-containing (meth)acrylate, etc.), and othercopolymerizable unsaturated monomers such as styrene, cyclohexyl vinylether, and dicyclopentadiene. By using these monomers in combination,the adherence, solvent solubility, and grafting rate of modifyingmonomers (A) and (B) can be enhanced further. Besides, the use level ofthese monomers is preferable not to exceed the sum of grafting amountsof modifying monomers (A) and (B).

[0033] It is possible to conduct the graft reaction using said modifyingmonomers (A) and (B) and other modifying monomers, and to obtain themodified polyolefin resin by publicly known methods. For example,solution method wherein polyolefin resin is dissolved into solvent suchas toluene under heating and modifying monomers are added, melt methodwherein modifying monomers are added together with molten polyolefinresin employing Banbury mixer, kneader, extruder, etc., and the like arementioned. The method of adding modifying monomers is not minded whetherthey are added one by one or added in a lump.

[0034] To the modified polyolefin resin of the invention, reaction aidfor improving the grafting efficiency of unsaturated carboxylic acid,stabilizer for adjusting the stability of resin, radical initiator forpromoting the reaction, and the like can be formulated additionally,depending on the purpose for use.

[0035] As the reaction aids, styrene, o-methylstyrene, p-methylstyrene,α-methylstyrene, divinylbenzene, hexadiene, dicyclopentadiene, etc. arementioned. As the stabilizers, hydroquinone, benzoquinone,nitrosophenylhydroxy compound, etc. can be mentioned. The radicalinitiator can be selected appropriately from publicly known products,but, for example, it is preferable to use organic peroxides such asbenzoyl peroxide, dicumyl peroxide, lauroyl peroxide, di-t-butylperoxide and cumene hydroperoxide.

[0036] The weight average molecular weight of modified polyolefin resinthus obtained is 15,000 to 150,000, preferably 30,000 to 120,000.Particularly preferable is 30,000 to 100,000. If under 15,000, then theadherent strength onto nonpolar substrates and the cohesive strengthbecome poor, and, if over 150,000, the workability, solubility intosolvent and compatibility with other resins decrease due to increasedviscosity.

[0037] Besides, as the measuring methods of weight average molecularweight, GPC method and light scattering method are known, and themolecular weight in the invention is molecular weight determined by GPCmethod. The grafting weight % of modifying monomers (A) is determined byalkali titration method, but, in the case of imide etc. wherein thederivatives have no acidic group, it is determined by FT-IR method.Also, the grafting weight % of modifying monomers (B) is determined byFT-IR method.

[0038] Moreover, the invention relates to a modified polyolefin resincomposition formulated with curing agent selected from epoxy,polyisocyanate, polyol and polyamine, or curing agent selected from oneswith those functional groups blocked with protective group, to saidmodified polyolefin resin.

[0039] As the epoxy curing agents, 1,2,3,4-diepoxybutane,1,2,7,8-diepoxyoctane, 1,2,9,10-diepoxydecane, vinylcyclohexenediepoxide, 1,2,5,6-diepoxycyclooctane,3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate,1,4-butanediol glycidyl ether, 1,6-hexanediol glycidyl ether,polyethyleneglycol glycidyl ether, polypropyleneglycol glycidyl ether,glycidyl hexahydrophthalate, glycidyl ester of dimeric acid, triglycidylisocyanurate, tetraglycidyldiaminodiphenylmethane, etc. are mentioned.

[0040] As the polyisocyanate curing agents, polyisocyanate curing agentssuch as ethylenediisocyanate, propylenediisocyanate,tetramethylenediisocyanate, hexamethylenediisocyanate,m-phenylenediisocyanate, p-phenylenediisocyanate,2,4-tolylenediisocyanate, 2,6-tolylenediisocyanate,1,5-naphthylenediisocyanate, 4,4′, 4″-triphenylmethanetriisocyanate,4,4′-diphenylmethanediisocyanate, m-xylylenediisocyanate, p-xylylenediisocyanate, isophoronediisocyanate and lysineisocyanate,polyisocyanate curing agents with two or more functionality obtainableby addition reaction or addition polymerization reaction of excess ofsaid polyisocyanate curing agent with low-molecular polyol, for example,ethylene glycol, propylene glycol, neopentyl glycol,2,2,4-trimethyl-1,3-pentanediol, hexamethylene glycol,cyclohexanedimethanol, trimethylolpropane, glycerine, pentaerythritol orthe like, polyisocyanate curing agents having Burette structure,polyisocyanate curing agents having allophanate structure,polyisocyanate curing agents having nurate structure, and curing agentswith isocyanate groups of said polyisocyanate curing agents blocked withprotective groups, called block isocyanates generally, are mentioned.

[0041] As the polyol curing agents, low-molecular polyol curing agentssuch as ethylene glycol, propylene glycol, neopentyl glycol,2,2,4-trimethyl-1,3-pentanediol, hexamethylene glycol,cyclohexanedimethanol, trimethylolpropane, glycerine andpentaerythritol, polyethylene glycol, polypropylene glycol,polytetrahydrofuran, copolymer of ethylene oxide with propylene oxide,hydrogenated polybutadiene with hydroxyl group at end, polyesterpolyolsobtainable from excess of said low-molecular polyols and dicarboxylicacids such as terephthalic acid, isophthalic acid, succinic acid, adipicacid, sebacic acid and hexahydroterephthalic acid, and the like arementioned.

[0042] As the polyamine curing agents, diethylenetriamine,triethylenetetramine, isophoronediamine, N-aminoethylpiperazine,m-xylylenediamine, diaminodiphenylmethane, melamine, methylolatedmelamine, etc. are mentioned. Also, polyhydrazide compounds such ascarbohydrazide, oxalic acid dihydrazide, succinic acid dihydrazide,glutamic acid dihydrazide, azelaic acid dihydrazide, undecanoic aciddihydrazide, maleic acid dihydrazide, itaconic acid dihydrazide andterephthalic acid dihydrazide can also be used similarly. Furthermore,curing agents with amino groups of said polyamine curing agents blockedwith protective groups, called block amines generally, are also used.

[0043] The formulation level of said curing agents can be selectedappropriately depending on the amount of functional groups (carboxylgroup, acid anhydride group, hydroxyl group, etc.) in the modifiedpolyolefin resin of the invention, but it is preferable to formulate soas the proportion of the number of said functional groups in themodified polyolefin resin that take part in the reaction to the numberof functional groups (e.g. numbers of isocyanate groups, hydroxyl groupsand amino groups) to become 10:1 to 1:5. In particular, a range from 5:1to 1:2 is preferable in the points of various physical properties offilm, in particular, adherence and gasohol resistance. If theformulation level of curing agent is higher than this range, theadherence decreases and, if too low, desired physical properties such asadherence, solvent resistance and water resistance cannot be obtained.Moreover, when formulating the curing agent, catalysts such as tin-basedcompounds can also be used in combination depending on the purpose.

[0044] The modified polyolefin resin of the invention can be used byitself or as a component for providing adherence in a variety of usessuch as adhesive, primer, paint and ink, and can be used in the formsadapted to uses such as solution, powder, paste and sheet. Moreover, atthat time, additives, for example, antioxidant, light stabilizer,ultraviolet absorber, pigment, dye, inorganic filler, etc. can beformulated, if need be. When using as a solution, aromatic solvents suchas toluene and xylene, aliphatic solvents such as cyclohexane,methylcyclohexane, ethylcyclohexane, heptane, nonane and decane, estersolvents such as ethyl acetate and butyl acetate, ketonic solvents suchas acetone, methyl ethyl ketone and methyl butyl ketone, alcoholicsolvents such as methanol, ethanol, propanol and butanol, or mixtures ofsaid solvents can be used, but, in view of the environmental problem, itis desirable not to use aromatic solvents. In particular, use ofmixtures of cyclohexane-based aliphatic solvents with ester or ketonicsolvents is preferable.

[0045] As the conditions of heat treatment when using the modifiedpolyolefin resin of the invention, it is laminated onto film at a hightemperature of around 170 to 180° C., or, after coating by spraying,brush coating, bar coating or the like in the state of solution, it isdried or baked at a temperature of around 80 to 100° C., or only driedat room temperature as it is for use.

[0046] When using as an adhesive or ink, not only nonpolar substratessuch as polyethylene and polypropylene, but also polar substrates suchas polyester, polyurethane, polyamide and aluminum are used very oftenin combination. Since the inventive modified polyolefin resin also hasthe adherence onto such polar substrates, it is suitable also for saiduse.

[0047] Also, when using as a primer or paint, the inventive modifiedpolyolefin resin is excellent in the adherence to upper paint and clearcoating, hence it is suitable for both polar substrates and nonpolarsubstrates.

[0048] When using as a paint or ink, other resins such as urethaneresin, epoxy resin, acrylic resin, phenol resin, alkyd resin, polyamideresin, polyimide resin, silicone resin and nitrocellulose, beingdifferent types from polyolefin resin, may be blended, if need be.

[0049] In these uses, when blending the inventive modified polyolefinresin with said additives and other different types of resins, it isrequired to formulate the inventive modified polyolefin resin in amountsof at least 5% by weight or more, specifically 30% by weight or more bysolids based on overall resin weight to maintain the adherence ontononpolar or polar substrates.

BEST EMBODIMENT TO PUT THE INVENTION INTO PRACTICE

[0050] In following, the invention will be illustrated in more detailbased on examples, but the invention is not confined thereto. Besides,the molecular weight was determined under the conditions of 40° C. and 1ml/min, making tetrahydrofuran as a developing solvent and using RI as adetector.

EXAMPLE 1

[0051] In a four-neck flask attached with stirrer, condenser anddropping funnel, 100 g of propylene-ethylene copolymer (propylenecomponent 97.5 mol %, ethylene component 2.5 mol %, weight averagemolecular weight 250,000) were dissolved into 400 g of toluene underheating. Then, while keeping the temperature of system at 110° C. andstirring, 1 g of dicumyl peroxide was added dropwise and, thereafter,the degradation treatment was performed for 1 hour. Next, 2 g ofaconitic anhydride, 4 g of octyl acrylate and 0.5 g of benzoyl peroxidewere added dropwise over 3 hours, respectively, and the mixture wasreacted further for 1 hour. After the reaction, the reaction product wascooled to room temperature and then purified by putting into a largequantity of acetone to obtain a modified polyolefin resin with weightaverage molecular weight of 68,000, grafting weight of aconiticanhydride of 1.2% by weight and octyl acrylate of 2.8% by weight.

EXAMPLE 2

[0052] Into a co-rotating twin screw extruder (from Technovel Co., Ltd.)with L/D=34 and φ=40 mm, 100 parts by weight ofpropylene-ethylene-α-olefin copolymer (propylene component 68 mol %,ethylene component 8 mol %, butene component 24 mol %, weight averagemolecular weight 50,000), 8 parts by weight of maleic anhydride, 8 partsby weight of lauryl methacrylate and 1.5 parts by weight of2,5-dimethyl-2,5-di(t-butylperoxy)hexane were charged. The reaction wasconducted under the conditions of retention time of 10 minutes andbarrel temperature of 180° C. (first barrel to seventh barrel), anddeaeration was performed at seventh barrel to remove residual unreactedmaterials. The weight average molecular weight of modified polyolefinresin obtained was 49,000, the grafting weight of maleic anhydride was5.2% by weight and the grafting weight of lauryl methacrylate was 6.2%by weight.

EXAMPLE 3

[0053] Into co-rotating twin screw extruder with L/D=34 and φ=40 mm, 100parts by weight of propylene-ethylene-α-olefin copolymer (propylenecomponent 68 mol %, ethylene component 8 mol %, butene component 24 mol%, weight average molecular weight 50,000), 12 parts by weight ofitaconic anhydride, 6 parts by weight of tridecyl acrylate and 2 partsby weight of lauroyl peroxide were charged. The reaction was conductedunder the conditions of retention time of 10 minutes and barreltemperature of 190° C. (first barrel to seventh barrel), and deaerationwas performed at seventh barrel to remove residual unreacted materials.The weight average molecular weight of modified polyolefin resinobtained was 47,000, the grafting weight of itaconic anhydride was 7.5%by weight and the grafting weight of tridecyl acrylate was 4.6% byweight.

EXAMPLE 4

[0054] In a four-neck flask attached with stirrer, condenser anddropping funnel, 100 g of propylene-ethylene copolymer (propylenecomponent 97.5 mol %, ethylene component 2.5 mol %, weight averagemolecular weight 250,000) were dissolved into 400 g of toluene underheating. Then, while keeping the temperature of system at 110° C. andstirring, 1 g of dicumyl peroxide was added dropwise and, thereafter,the degradation treatment was performed for 1 hour. Next, 15 g ofcitraconic anhydride, 20 g of stearyl methacrylate and 0.5 g of benzoylperoxide were added dropwise over 3 hours, respectively, and the mixturewas reacted further for 1 hour. After the reaction, the reaction productwas cooled to room temperature and then purified by putting into a largequantity of acetone to obtain a modified polyolefin resin with weightaverage molecular weight of 76,000, grafting weight of citraconicanhydride of 9.4% by weight and grafting weight of stearyl methacrylateof 13.8% by weight.

EXAMPLE 5

[0055] Into a co-rotating twin screw extruder with L/D=34 and φ=40 mm,100 parts by weight of propylene-ethylene-α-olefin copolymer (propylenecomponent 68 mol %, ethylene component 8 mol %, butene component 24 mol%, weight average molecular weight 50,000), 4 parts by weight ofitaconic anhydride, 2 parts by weight of octyl methacrylate, 2 parts byweight of stearyl methacrylate and 1.5 parts by weight of di-t-butylperoxide were charged. The reaction was conducted under the conditionsof retention time of 10 minutes and barrel temperature of 160° C. (firstbarrel to seventh barrel), and deaeration was performed at seventhbarrel to remove residual unreacted materials. The weight averagemolecular weight of modified polyolefin resin obtained was 45,000, thegrafting weight of itaconic anhydride was 2.6% by weight, and sum of thegrafting weights of octyl methacrylate and stearyl methacrylate was 3.0%by weight.

COMPARATIVE EXAMPLE 1

[0056] In a four-neck flask attached with stirrer, condenser anddropping funnel, 100 g of propylene-ethylene copolymer (propylenecomponent 97.5 mol %, ethylene component 2.5 mol %, weight averagemolecular weight 250,000) were dissolved into 400 g of toluene underheating. Then, while keeping the temperature of system at 110° C. andstirring, 1 g of dicumyl peroxide was added dropwise and, thereafter,the degradation treatment was performed for 1 hour. Next, 2 g ofaconitic anhydride and 0.5 g of benzoyl peroxide were added dropwiseover 3 hours, respectively, and the mixture was reacted further for 1hour. After the reaction, the reaction product was cooled to roomtemperature and then purified by putting into a large quantity ofacetone to obtain a modified polyolefin resin with weight averagemolecular weight of 49,000 and grafting weight of aconitic anhydride of1.1% by weight.

COMPARATIVE EXAMPLE 2

[0057] Into a co-rotating twin screw extruder with L/D=34 and φ=40 mm,100 parts by weight of propylene-ethylene-α-olefin copolymer (propylenecomponent 68 mol %, ethylene component 8 mol %, butene component 24 mol%, weight average molecular weight 50,000), 50 parts by weight ofitaconic anhydride, 6 parts by weight of tridecyl acrylate and 2 partsby weight of lauroyl peroxide were charged. The reaction was conductedunder the conditions of retention time of 10 minutes and barreltemperature of 170° C. (first barrel to seventh barrel), and deaerationwas performed at seventh barrel to remove residual unreacted materials.The weight average molecular weight of modified polyolefin resinobtained was 18,000, the grafting weight of itaconic anhydride was 22.6%by weight and the grafting weight of tridecyl acrylate was 3.1% byweight.

COMPARATIVE EXAMPLE 3

[0058] Into a co-rotating twin screw extruder with L/D=34 and φ=40 mm,100 parts by weight of propylene-ethylene-α-olefin copolymer (propylenecomponent 68 mol %, ethylene component 8 mol %, butene component 24 mol%, weight average molecular weight 50,000), 12 parts by weight ofitaconic anhydride, 200 parts by weight of tridecyl acrylate and 2 partsby weight of lauroyl peroxide were charged. The reaction was conductedunder the conditions of retention time of 10 minutes and barreltemperature of 170° C. (first barrel to seventh barrel), and deaerationwas performed at seventh barrel to remove residual unreacted materials.The solvent-insolbles occupied a greater part, which was impossible touse.

COMPARATIVE EXAMPLE 4

[0059] Into a co-rotating twin screw extruder with L/D=34 and φ=40 mm,100 parts by weight of propylene-ethylene-α-olefin copolymer (propylenecomponent 68 mol %, ethylene component 8 mol %, butene component 24 mol%, weight average molecular weight 50,000), 8 parts by weight of maleicanhydride, 8 parts by weight of methyl methacrylate and 1.5 parts byweight of Perbutyl I (from Nippon Oil and Fats Co.) were charged. Thereaction was conducted under the conditions of retention time of 10minutes and barrel temperature of 150° C. (first barrel to seventhbarrel), and deaeration was performed at seventh barrel to removeresidual unreacted materials. The weight average molecular weight ofmodified polyolefin resin obtained was 47,000, the grafting weight ofmaleic anhydride was 4.7% by weight and the grafting weight of methylmethacrylate was 6.4% by weight.

COMPARATIVE EXAMPLE 5

[0060] Into a co-rotating twin screw extruder with L/D=34 and φ=40 mm,100 parts by weight of propylene-ethylene-α-olefin copolymer (propylenecomponent 68 mol %, ethylene component 8 mol %, butene component 24 mol%, weight average molecular weight 50,000), 8 parts by weight of maleicanhydride, 8 parts by weight of 2-ethylstearylacrylate and 1.5 parts byweight of dicumyl peroxide were charged. The reaction was conductedunder the conditions of retention time of 10 minutes and barreltemperature of 180° C. (first barrel to seventh barrel), and deaerationwas performed at seventh barrel to remove residual unreacted materials.The weight average molecular weight of modified polyolefin resinobtained was 47,000, the grafting weight of maleic anhydride was 4.5% byweight and the grafting weight of 2-ethylstearyl acrylate was 6.5% byweight.

[0061] [Test 1 (Solvent Solubility)]

[0062] Of the modified polyolefin resins obtained in Examples 1 through5 and Comparative examples 1 through 5, 10% by weight toluene solutions,20% by weight ethylcyclohexane solutions and 20% by weight n-hexanesolutions were prepared at 70 to 80° C. After cooled to roomtemperature, these were allowed to stand statically to evaluate thesolvent solubility. The results are shown in Table 1.

[0063] (Table 1) TABLE 1 Test results Solvent solubility Sample TolueneEthylcyclohexane n-Hexane Example 1 ◯ ◯ ◯ 2 ◯ ◯ ◯ 3 ◯ ◯ ◯ 4 ◯ ◯ ◯ 5 ◯ ◯◯ Comparative Δ˜X X X example 1 2 Δ˜X Δ˜X Δ˜X 3 X X X 4 Δ˜X Δ˜X Δ˜X 5◯˜Δ Δ Δ

[0064] [Test 2 (Adhesiveness Test)]

[0065] Of the modified polyolefin resins obtained in Examples 1 through5 and comparative examples 1 through 5, two types of samples of 10% byweight toluene solutions and 20% by weight ethylcyclohexane/methyl ethylketone (=8/2) solutions were prepared, respectively, and following testswere performed. The results shown in Table 2 and Table 3. (Besides, themodified polyolefin resin obtained in Comparative example 3 wasinsoluble into solvent because of the presence of gel and ultrahighmolecular weight material produced by crosslinking, hence followingtests could not be performed).

[0066] Tack Test

[0067] Each sample was coated onto a high-density polyethylene film andpolypropylene film without surface treatment, using #20 Meyer bar, whichwas dried for 15 hours at room temperature. The specimen was folded soas the coated surfaces to overlap and, after pressed down lightly withfingers, it was peeled off to evaluate the tack from the peelingliability.

[0068] Adherence Test of Film at Room Temperature

[0069] For a painted film obtained by drying for 15 hours at roomtemperature similarly to the tack test, cellophane adhesive tape wasstuck closely on the surface of film and then peeled off in thedirection of 180 degrees to observe the situation of the surface ofremaining coated film.

[0070] Adherence Test

[0071] Each sample was spray coated onto an ultrahigh moduluspolypropylene plate so as the thickness of dried film to become not lessthan 10 μm and not more than 15 μm, which was dried for 30 minutes at80° C. After the specimen was allowed to stand statically for 3 days atroom temperature, slits reaching the base were engraved on the surfaceof coated film with cutter to make 100 cross-cuts at intervals of 1 mm.Then, cellophane adhesive tape was stuck closely thereon and peeled offfive times in the direction of 180 degrees to count the number ofremaining cross-cuts (X). The result was expressed as remaining numberper 100 cross-cuts prepared (X/100).

[0072] Heat Seal Strength Test

[0073] Each sample was coated onto a polypropylene film after coronasurface treatment using #20 Meyer bar, which was dried for 15 hours atroom temperature. The coated surfaces were superposed between themselvesand heat sealed under the conditions of 1.5 kg/cm², 90° C. and 10 secusing No.276 Heat Seal Tester (from Yasuda Seiki Seisakusho). Eachspecimen was cut so as the width to become 1 cm and peeled off under theconditions of 5 kg weight and 100 mm/min using tensile tester to measurethe peeling strength thereof. Tests were made three times and the resultwas expressed by the average value.

[0074] (Table 2) TABLE 2 Test results (Toluene solution) Adherence offilm at room temperature Heat seal Left: High-density Adherence strengthPolyethylene Sample ×/100 (g/cm) Tack Right; Polypropylene Example 1100/100 1000 None Δ, Δ 2 100/100 1100 None ◯, ◯ 3 100/100 1030 None ◯, ◯4 100/100 1200 None Δ, Δ 5 100/100 1100 None Δ, ◯ Comparative  85/100500 Strong X, Δ example 1 2  90/100 520 Strong X, X 4  75/100 550 WeakX, Δ 5  90/100 820 Strong X, Δ

[0075] Samples of Examples 1 through 5 after measurement of heat sealstrength showed that the peeling surface was not from the substrate, butfrom the inside of adhesive layer.

[0076] (Table 3) TABLE 3 Test results (Ethylcyclohexane/methyl ethylketone solution) Adherence of film at room temperature Heat seal Left:High-density Adherence strength Polyethylene Sample ×/100 (g/cm) TackRight; Polypropylene Example 1 100/100 1100 None Δ, Δ 2 100/100 1250None ◯, ◯ 3 100/100 1100 None ◯, ◯ 4 100/100 1200 None Δ, Δ 5 100/1001050 None Δ, ◯ Comparative  90/100 600 Strong X, Δ example 1 2  90/100450 Strong X, X 4  70/100 550 Weak X, Δ 5  85/100 800 Strong X, Δ

[0077] Samples of Examples 1 through 5 after measurement of heat sealstrength showed that the peeling surface was not from the substrate, butfrom the inside of adhesive layer.

[0078] [Test 3 (Paint Test)]

[0079] Of the modified polyolefin resins obtained in Examples 1 through5 and comparative examples 1 through 5, two types of samples of 40% byweight toluene solutions and 40% by weight ethylcyclohexane/methyl ethylketone (=8/2) solutions were prepared, respectively, and paints wereprepared using following formulation as binder resins.

[0080] Binder resin (each sample): 100 parts by weight

[0081] Alkyd resin (Phthalkyd V904, from Hitachi Chemical Co.)

[0082] 15 parts by weight

[0083] TiO₂: 5 parts by weight

[0084] Carbon black: 1 part by weight

[0085] Rouge: 2 parts by weight

[0086] Talc: 15 parts by weight

[0087] Silica delustering agent: 5 parts by weight

[0088] After each of said compositions was kneaded for about 1 hour in asand mill, it was diluted with toluene for toluene sample and withethylcyclohexane/methyl ethyl ketone (=8/2) for ethylcyclohexane/methylethyl ketone sample so as the viscosity to become 12 to 13 sec/20° C.through Ford cup #4 for preparation. Each paint was spray coated onto anultrahigh modulus polypropylene plate so as the thickness of dried filmto become not less than 30 μm and not more than 35 μm, which was driedfor 30 minutes at room temperature and then baked for 30 minutes at 80°C. After the specimen was allowed to stand statically for 48 hours atroom temperature, following tests were performed. The results are shownin Table 4 and Table 5.

[0089] Adherence Test

[0090] Cross-cuts test similar to Test 2 was performed.

[0091] Warm Water Resistance Test

[0092] The specimen was soaked for 240 hours into warm water of 40° C.and the state of coated film was observed visually. In addition, theadherence test by cross-cuts test was performed.

[0093] Gasoline Resistance Test

[0094] A scratch (X mark) reaching the base was engraved on the surfaceof each coated film with cutter knife and the specimen was soaked intogasoline to visually observe the state of coated film.

[0095] (Table 4) TABLE 3 Test results (Toluene solution) Adherence Warmwater Sample ×/100 resistance Gasoline resistance Example 1 100/100 Noabnormality After 2-hr soaking, 100/100 no abnormality 2 100/100 Noabnormality After 2-hr soaking, 100/100 no abnormality 3 100/100 Noabnormality After 2-hr soaking, 100/100 no abnormality 4 100/100 Noabnormality After 2-hr soaking, 100/100 no abnormality 5 100/100 Noabnormality After 2-hr soaking, 100/100 no abnormality Comparative 85/100 No abnormality After 2-hr soaking, example 1  85/100 noabnormality 2  90/100 Blister generation After 2-hr soaking,  90/100 noabnormality 4  80/100 No abnormality After 2-hr soaking,  75/100 blistergeneration 5  90/100 No abnormality After 2-hr soaking,  90/100 noabnormality

[0096] Because of solvent insolubility, Comparative example 3 wasimpossible to evaluate.

[0097] (Table 5) TABLE 5 Test results (Ethylcyclohexane/methyl ethylketone solution) Adherence Warm water Sample ×/100 resistance Gasolineresistance Example 1 100/100 No abnormality After 2-hr soaking, 100/100no abnormality 2 100/100 No abnormality After 2-hr soaking, 100/100 noabnormality 3 100/100 No abnormality After 2-hr soaking, 100/100 noabnormality 4 100/100 No abnormality After 2-hr soaking, 100/100 noabnormality 5 100/100 No abnormality After 2-hr soaking, 100/100 noabnormality Comparative  80/100 No abnormality After 2-hr soaking,example 1  70/100 no abnormality 2  80/100 Blister generation After 2-hrsoaking,  75/100 no abnormality 4  70/100 No abnormality After 2-hrsoaking,  65/100 blister generation 5  85/100 No abnormality After 2-hrsoaking,  75/100 no abnormality

[0098] Because of solvent insolubility, Comparative example 3 wasimpossible to evaluate.

[0099] [Test 4 (Primer Test)]

[0100] Of the modified polyolefin resins obtained in Examples 1 through5 and Comparative examples 1 through 5, two types of samples of 10% byweight toluene solutions and 20% by weight ethylcyclohexane/methyl ethylketone (=8/2) solutions were prepared, respectively. Each sample wasspray coated onto an ultrahigh modulus polypropylene plate so as thethickness of dried film to become not less than 10 μm and not more than15 μm, which was dried for 30 minutes at 80° C. Next, a two-componenttype upper white paint was spray coated so as the thickness of driedfilm to become not less than 45 μm and not more than 50 μm, which wasallowed to stand statically for 15 minutes at room temperature and thenbaked for 30 minutes at 90° C. After the specimen was allowed to standstatically for 3 days at room temperature, tests similar to Test 3 wereperformed. The results are shown in Table 6 and Table 7.

[0101] (Table 6) TABLE 6 Test results (Toluene solution) Adherence Warmwater Sample ×/100 resistance Gasoline resistance Example 1 100/100 Noabnormality After 2-hr soaking, 100/100 no abnormality 2 100/100 Noabnormality After 2-hr soaking, 100/100 no abnormality 3 100/100 Noabnormality After 2-hr soaking, 100/100 no abnormality 4 100/100 Noabnormality After 2-hr soaking, 100/100 no abnormality 5 100/100 Noabnormality After 2-hr soaking, 100/100 no abnormality Comparative 80/100 No abnormality After 2-hr soaking, example 1  80/100 noabnormality 2  80/100 Blister generation After 2-hr soaking,  80/100 noabnormality 4  80/100 No abnormality After 2-hr soaking,  85/100 blistergeneration 5  85/100 No abnormality After 2-hr soaking,  85/100 noabnormality

[0102] Because of solvent insolubility, Comparative example 3 wasimpossible to evaluate.

[0103] (Table 7) TABLE 7 Test results (Ethylcyclohexane/methyl ethylketone solution) Adherence Warm water Sample ×/100 resistance Gasolineresistance Example 1 100/100 No abnormality After 2-hr soaking, 100/100no abnormality 2 100/100 No abnormality After 2-hr soaking, 100/100 noabnormality 3 100/100 No abnormality After 2-hr soaking, 100/100 noabnormality 4 100/100 No abnormality After 2-hr soaking, 100/100 noabnormality 5 100/100 No abnormality After 2-hr soaking, 100/100 noabnormality Comparative  80/100 No abnormality After 2-hr soaking,example 1  80/100 no abnormality 2  80/100 Blister generation After 2-hrsoaking,  10/100 no abnormality 4  80/100 No abnormality After 2-hrsoaking,  85/100 blister generation 5  85/100 No abnormality After 2-hrsoaking,  85/100 no abnormality

[0104] Because of solvent insolubility, Comparative example 3 wasimpossible to evaluate.

[0105] [Test 5 (Ink Test)]

[0106] Of the modified polyolefin resins obtained in Examples 1 through5 and Comparative examples 1 through 5, samples of 40% by weightethylcyclohexane/butyl acetate (70/30, weight ratio) solutions wereprepared, respectively, and inks were prepared using followingformulation as binder resins.

[0107] Binder resin (each sample): 100 parts by weight

[0108] Urethane resin for ink: 50 parts by weight

[0109] TiO₂: 100 parts by weight

[0110] Ethyl acetate: 100 parts by weight

[0111] Isopropyl alcohol: 50 parts by weight

[0112] Each of said compositions was milled in a paint shaker to preparewhite printing ink. The printing ink obtained was coated onto each filmof oriented polypropylene (OPP), high-density polyethylene (HDPE),poly(ethylene terephthalate) (PET) and nylon (NY) using #12 Meyer bar.Cellophane tape was stuck on the coated surface and the state of coatedsurface when peeling off rapidly was observed visually. Moreover, fromthe state of solution after milling and the state of dried film, thecompatibility was evaluated. The results are shown in Table 8.

[0113] (Table 8) TABLE 8 Test results Adhesiveness Sample compatibilityOPP HDPE PET NY Example 1 ◯ ◯ Δ ◯ ◯ 2 ◯ ◯ ◯ ◯ ◯ 3 ◯ ◯ ◯ ◯ ◯ 4 ◯ ◯ Δ ◯ ◯5 ◯ ◯ Δ ◯ ◯ Comparative example 1 X ◯ X ◯ ◯ 2 Δ Δ X ◯ ◯ 4 X ◯ X ◯ ◯ 5 Δ◯ X ◯ ◯

[0114] [Test 6]

[0115] Into 100 g of 10% by weight toluene solution of the modifiedpolyolefin resin obtained in Example 2 were formulated curing agentsshown in table at fixed levels, which were dissolved homogeneously. Witheach sample, heat seal strength test similar to Test 2 and primer testsimilar to Test 4 were implemented. In addition, gasohol resistance testwas performed using gasohol (gasoline/ethanol=9/1) in place of gasolineused in the gasoline resistance test. The results are shown in Table 9.TABLE 9 Test results Type of cur- ing agent Heat seal Primer test(formulation strength. Warm water Gasoline Gasohol level g) (g/cm)Adherence resistance resistance resistance 1,6-hexane- Destruction100/100 No abnor- After 2-hr After 2 hrs, diol glycidyl of materialmality soaking, no no abnor- ether (0.6) 100/100 abnormality malityIsophoronedi- Destruction 100/100 No abnor- After 2-hr After 2 hrs,isocyanate *1 of material mality soaking, no no abnor- (0.6) 100/100abnormality mality Polytail Destruction 100/100 No abnor- After 2-hrAfter 2 hrs, HA*2(8.0) of material mality soaking, no no abnor- 100/100abnormality mality m-Xylylene Destruction of 100/100 No abnor- After2-hr After 2 hrs, diamine (0.4) material mality soaking, no no abnor-100/100 abnormality mality

UTILIZABILITY IN THE INDUSTRY

[0116] The modified polyolefin resin of the invention exerts followingeffects over the conventional one.

[0117] (1) It has no tack and is excellent in the adherence.

[0118] (2) It is excellent in the solubility not only into aromaticsolvents, but also into nonaromatic solvents.

[0119] (3) It is excellent in the compatibility with other resins ofdifferent kinds.

[0120] (4) In particular, based on that the peeling surface of sampleafter measurement of heat seal strength is not from substrate, but frominside of adhesive layer, it has strong adherent strength onto nonpolarsubstrates.

[0121] (5) When formulating curing agent, the solvent resistance(gasohol resistance) improves. In addition, in the heat seal strength,strength as high as the substrate film is destroyed is exerted.

[0122] From the points as above, The modified polyolefin resin of theinvention is useful particularly for adhesive, primer, paint and ink.

SUMMARY

[0123] The invention is to provide a resin that has excellent adherenceonto nonpolar substrates and combines the attributes of no tack, goodsolubility into aromatic solvents and non-aromatic solvents and goodcompatibility with other resins.

[0124] A modified polyolefin resin with polyolefin resin graft modifiedwith unsaturated polycarboxylic acid or its derivative (A) and(meth)acrylic ester (B) represented by a specific general formula, withcontents of (A) and (B) of 0.1 to 20% by weight and 0.1 to 30% byweight, respectively, in modified polyolefin resin, and with its weightaverage molecular weight of 15,000 to 150,000.

1. A modified polyolefin resin with polyolefin resin graft modified withunsaturated polycarboxylic acid or its derivative (A) and (meth)acrylicester (B) represented by a following general formula, with contents of(A) and (B) of 0.1 to 20% by weight and 0.1 to 30% by weight,respectively, in modified polyolefin resin, and with weight averagemolecular weight of 15,000 to 150,000. CH₂═CR₁COOR₂  (Chemicalformula 1) (wherein R₁═H or CH₃, R₂═C_(n)H_(2n+1), n=integer of 8 to 18)2. The modified polyolefin resin of claim 1, wherein said unsaturatedpolycarboxylic acid or its derivative (A) is itaconic anhydride and/ormaleic anhydride.
 3. The modified polyolefin resin of claim 1 or 2,wherein said (meth)acrylic ester (B) is at least one kind selected fromoctyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate andstearyl (meth)acrylate.
 4. The modified polyolefin resin of any ofclaims 1 through 3, wherein said polyolefin resin is at least one kindselected from ethylene-propylene copolymer, propylene-butene copolymerand ethylene-propylene-butene copolymer.
 5. A modified polyolefin resincomposition characterized by formulating curing agent selected fromepoxy, polyisocyanate, polyol, polyamine and curing agents with thosefunctional groups blocked with protective group, to the modifiedpolyolefin resin of any of claims 1 through
 4. 6. An adhesive containingmodified polyolefin resin of any of claims 1 through 4 or modifiedpolyolefin resin composition of claim
 5. 7. A primer containing modifiedpolyolefin resin of any of claims 1 through 4 or modified polyolefinresin composition of claim
 5. 8. A paint containing modified polyolefinresin of any of claims 1 through 4 or modified polyolefin resincomposition of claim
 5. 9. An ink containing modified polyolefin resinof any of claims 1 through 4 or modified polyolefin resin composition ofclaim 5.